The electrode-liquid interface is the most common interface encountered in electrochemical systems and is of great and diverse technological importance. At the molecular level, surface atoms have a different chemical environment than those present in the bulk environment. Thus, a direct observation and fundamental understanding of charge transport, phase transitions, growth of solid interfaces (e.g., adlayers), and reactivity at the electrode-electrolyte interface are needed. The term “adlayer” refers to adsorbed chemical species that form layers on the surface of the electrode and chemically interact with the electrode or substrate. While surface science techniques have made investigation of adsorbed molecules possible, molecular-scale surface science studies are conducted primarily at solid-gas interfaces and solid-vacuum interfaces due to challenges associated with applying surface-sensitive vacuum techniques to high volatility liquids. Consequently, detailed in-situ studies at the electrode-solution interface using surface-sensitive techniques are especially lacking. Ex-situ electrochemical experiments involve removing an electrode from an electrolyte and analyzing sample adlayers present on the electrode in an ambient atmosphere or in an ultra-high vacuum (UHV) instrument or system. However, even well-characterized emersion adlayers may only partially or incompletely represent the real in-situ system. Further, in-situ chemical imaging of actual electrode-electrolyte interfaces has not yet been achieved. Thus, there remains a need for in-situ measurements of electrochemical systems that probe the electrode-liquid sample or liquid interface rather than relying on ex-situ analyses. In addition, new chemical imaging approaches are needed that employ vacuum-based techniques suitable for study of surfaces of high-vapor-pressure liquids and electrode-solution interfaces. The present invention addresses these needs.